Acetamides



United States Patent 3,525,767 ACETAMIDES Kenneth Wayne Ratts, CreveCoeur, and Angelina Ngo Yao, University City, Mo., assignors to MonsantoCompany, St. Louis, Mo., a corporation of Delaware N0 Drawing. Filed May11, 1966, Ser. No. 549,150

Int. Cl. C07c 103/56 US. Cl. 260-561 7 Claims ABSTRACT OF THE DISCLOSUREThis invention relates to sulfur containing acetamides. The sulfurcontaining acetamides of this invention are represented by the formulaRCH: O RZXI,

S=OHCN R cHz R Xb wherein R and R are each selected from the groupconsisting of hydrogen, alkyl of not more than 12 carbon atoms andhaloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogenatoms, R and R are each selected from the group consisting of alkyl ofnot more than 12 carbon atoms, alkeuyl of not more than 12 carbon atomsand phenyl, X and X are halogen (Cl, Br, F and I), and a and b are eachintegers from O to 5 inclusive.

In the above formula R and R can be hydrogen, alkyl such as methyl,ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, tert-butyl,amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the varioushomologues and isomers of alkyl having from 1 to 12 carbon atoms andhaloalkyl such as chloromethyl, iodomethyl, bromomethyl, fluoromethyl,chloroethyl, iodoethyl, bromoethyl, fiuoroethyl, trichloromethyl,triiodomethyl, tribromomethyl, trifluoromethyl, dichloroethyl,chloro-n-propyl, bromo-n-propyl, iodoisopropyl, bromo-n-butyl,bromo-tert-butyl, 1,3,3-trichlorobutyl, 1,3,3-tribromobutyl,chloropentyl, bromopentyl, 2,3-dichloropentyl, 3,3-dibromopentyl,chlorohexyl, bromohexyl, 2,4-dichlorohexyl, 1,3-dibromohexyl,1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoroheptyl,1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-di (chloromethyDheptyl,chlorooctyl, bromooctyl, iodooctyl, 2,4 di(chloromethyl)hexyl, 2,4dichlorooctyl, 2,4,4 tri (chloromethyl)pentyl, 1,3,5-tribromooctyl andthe halogenated straight and branched chain nonyl, decyl, undecyl anddodecyl.

In the above formula the group can be, for example: dimethylamino,diethylamino, dipropylamino, dibutylamino, dihexylamino, dioctylamino,didodecylamino, di(tert-butyl)amino, divinylamino, diallylamino,dibutenylarnino, diheptenylamino, didodecenylamino,di(chloromethyl)amino, di(2-chlorobutyl)amino, di(2-fluorobutyl)amino,di(bromomethyl)amino, di (2,2,4-trichlorooctyl)amino,di(2-chloro-2-buten 1 yl) amino, di(2 bromo-Z-propen-l-yl)amino,N-methyl-N- butylamino, N-methyl-N-butenylamino,N(chloromethyl)-N-propylamino, diphenylamino,di(2,4-dichlorophenyl)amino, di(2,6-dichlorophenyl)amino,di(2,4,5-trichlorophenyDamino, di(2,6-dibromophenyl)amino,di(4-iodophenyl)amino, di(2 fluorophenyDamino, di(2,3,4,5,6-

3,525,767 Patented Aug. 25, 1970 pentachlorophenyl)amino,di(4-chlorophenyl)amino, and di (2,4,6-tribromopheuyl) amino.

The sulfur containing acetamides of the present invention are preparedby a process which comprises reacting a sulfonium salt of the formulawherein R, R R R X, X a and b are as defined above with a substantiallyequimolar amount of an alkaline material in the presence of an inertsubstantially non-aqueous liquid media. The process is suitably carriedout at room temperature, i.e. about 15 C. to about 25 C. However, higheror lower temperatures can be used, the temperature not being critical.Pressure is likewise not a critical factor in the process of thisinvention. Pressure both above and below atmospheric pressure can beemployed although atmospheric pressure is preferred for convenience.

Alkaline materials suitable for use in the process of this inventioninclude inorganic bases, for example, alkali metal hydroxides such aslithium hydroxide, sodium hydroxide, potassium hydroxide, rubidiumhydroxide and cesium hydroxide; alkaline earth metal hydroxides such ascalcium hydroxide and barium hydroxide; alkali metal hydrides such assodium hydride, potassium hydride and lithium hydride; metallic oxidessuch as calcium oxide, magnesium oxide, silver oxide and barium oxide;alkali metal and alkaline earth metal carbonates such as sodiumcarbonate, potassium carbonate, magnesium carbonate, calcium carbonateand barium carbonate, and ammonia and ammonia producing compounds suchas ammonium hydroxide and ammonium carbonate; and organic bases, forexample, aliphatic and aromatic alkoxides such as sodium methoxide,potassium methoxide, lithium methoxide, sodium ethoxide, potassiumethoxide, lithium butoxide, sodium butoxide, sodium phenoxide, lithiumphenox ide and potassium phenoxide, primary, secondary and tertiaryamines such as methylamine, ethylamine, propylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,diisobutylamine, di-secbutylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, N-methyl-N-ethylamine,N-methyl-N-isopropylamine, trimethylamine, triethylamine,tri-n-propylamine, triisopropylamine, tri-nbutylamine,tri-isobutylamine, tri-sec-butylamine, tri-namylamine, triisoamylamine,trihexylamine, triheptylamine and trioctylamine; other amines such aspyridine and morpholine, and mercaptides such as sodiummethylmercaptide, sodium ethylmercaptide, potassium methylmercaptide andpotassium phenylmercaptide.

'Inert liquid media which can be used in the process of this inventioninclude, for example, alcohols such as methyl alcohol, ethyl alcohol,propyl alcohol, and the like, tetrahydrofuran and ethers such asdiglyme, diethyl ether, and the like. An excess of amine reactant alsoserves as inert liquid media.

The separation of the product from the reaction mixture is readilyaccomplished. For example the salt, such as an alkali metal halogen saltformed during the reaction, can be separated from the product containingreacin many organic solvents, for example alcohols, ketones,hydrocarbons such as benzene, toluene, xylene and the like andchlorohydrocarbons such as chlorobenzene, carbon tetrachloride and thelike.

The following examples illustrate the invention. In the followingexamples as well as in the specification and appended claims, parts andpercent are by weight unless otherwise indicated.

EXAMPLE 1 A suitable reaction vessel is charged with about 12 parts ofdimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride and 250 parts oftetrahydrofuran and then 2.3 parts of sodium hydride are added withstirring at room temperature (about 25 C.). After a substantiallyequimolar amount of hydrogen evolves, the sodium bromide is removed byfiltration and the tetrahydrofuran by evaporation under reduced pressureto give about 8.0 parts of N,N-diethyl a(dimethylsulfuranylidene)acetamide.

Following substantially the same procedure as in Example 1 above thefollowing sulfur containing acetamides of this invention are preparedExample:

2 N,N dimethyl a (dimethylsulfuranylidene) acetamide.

3 N,N dibutyl oz (dimethylsulfuranylidene) acetamide.

4 N,N-di-n-buten 1 yl a (dimethylsulfuranylidene) acetamide.

5 N,N diphenyl on (di-n-butylsulfuranylidene) acetamide.

6 N,N-dichloromethyl a [di(2,4-dichlorobutyl)sulfuranylidene] acetamide.

7 N methyl N phenyl-a-(dimethylsulfuranylidene) acetamide.

8 N,N difluoromethyl a (dimethylsulfuranylidene) acetamide.

9 H... N,N di(2,4 dichlorophenyl)-a-dimethylsulfuranylidene) acetamide.

l N,N dimethyl a (di-2-chloroethylsulfuranylidene) acetamide.

11 N,N dimethyl a (didodecylsulfuranylidene) acetamide.

12 N,N didodecyl oz dimethylsulfuranylidene) acetamide.

The sulfur containing acetamides of this invention are useful per se forvarious purposes such as fire retardants, rust inhibitors, rustremovers, tanning agents, and as chemical intermediates for petroleumadditives and agricultural chemicals. For example, the sulfur containingacetamides of this invention are useful in the preparation of nitronesin accordance with the following representative synthesis RCHz o mxs=o11 "m Q-NO 3 0112 B x. R R

0 0 R 20. gl i CHi lN R R R Xb wherein R, R R R X, X a and b are asdefined above and R is halogen or lower alkyl, R is N0 or lower alkoxy,n is an integer from 0 to 5 and m is an integer from 0 to 2. The processis usually carried out with substantially equimolar amounts of reactantsin the presence of an inert organic medium such as an aromatichydrocarbon at a temperature from about 0 C. to about 75 C. The abovenitrones and more detailed processes for preparing them are disclosedand claimed in applica- 4 tion Ser. No. 549,153, filed of even dateherewith, and now abandoned.

The sulfur containing acetamide salts used as starting materials in thepreparation of the compounds of this invention can be prepared by theprocess disclosed in application Ser. No. 467,750, filed June 28, 1965,now US. Pat. No. 3,478,154. Said process comprises reacting a sulfide ofthe formula RCH SCH R wherein R and R are as defined above with asubstan tially equimolar amount of an u-haloacetamide of the formula 0 RX XOH2( i-N R Xb wherein R R X, X a and b are as defined above in thepresence of an inert liquid medium at a temperature below thedecomposition temperature of the sulfide employed.

Although the invention is described with respect to specificmodifications, the details thereof are not to be construed aslimitations except to the extent indicated in in the following claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. Compound of the formula wherein R and R are each selected from thegroup consisting of hydrogen, alkyl of not more than 12 carbon atoms andhaloalkyl of not more than 12 carbon atoms containing from 1 to 3halogen atoms, R and R are each selected from the group consisting ofalkyl of not more than 12 carbon atoms, alkenyl of not more than 12carbon atoms and phenyl, X and X are halogen and a and b are eachintegers from '0 to 5 inclusive.

2. Compound of claim 1 wherein R and R are hydrogen.

3. Compound of claim 1 which is N,N-diethyl-u-(dimethylsulfuranylideneacetamide.

4. Compound of claim 1 which isN,N-dimethyl-a-(dimethylsulfuranylidene)acetamide.

5. Compound of claim 1 which isN,N-diphenyl-a-(din-butylsulfuranylidene) acetamide.

6. Compound of claim 1 which is N,N-di(2,4-dichlorophenyl -a-(dimethylsulfuranylidene) acetamide.

7. A compound containing up to 15 carbon atoms of the formula:

References Cited UNITED STATES PATENTS 3,397,223 8/1968 Payne 260464ALEX MAZEL, Primary Examiner I. A. NARCAVAGE, Assistant Examiner US. Cl.X.R.

